Dyeing keratinic fibers and human hair with para-diamines and couplers

ABSTRACT

THE INVENTION RELATES TO DYEING KERATINIC FIBERS WITH A 1-AMINO-4-AMINO-BENZENE WHICH CAN HAVE HALOGEN, ALKYL OR ALKOXY GROUPS ON THE BENZENE RING AND A COUPLER SELECTED FROM THE GROUP CONSISTING OF SUBSTITUTED PHENOLS, R3CO-CH2-COR4 AND   1-Z,3-CH3-2-PYRAZOLIN-5-ONE   IN WHICH R3 AND R4 ARE BOTH -CH3,R3 IS -CH3 AND R4 IS -OC2H5 AND R3 IS PHENYL AND R4 IS   -NH-(1,4-PHENYLENE)-COOH OR -NH-(1,3-PHENYLENE)-COOH   AND Z IS A SULPHOPHENYL OR CHLORO-SULPHOPHENYL.

United States Patent ()flice 3,563,684 Patented Feb. 16, 1971 Int. Cl. A61k 7/12 US. Cl. 8-11 7 Claims ABSTRACT OF THE DISCLOSURE The invention relates to dyeing keratinic fibers with a l-amino-4-amino-benzene which can have halogen, alkyl or alkoxy groups on the benzene ring and a coupler selected from the group consisting of substituted phenols, R COCH COR and in which R and R are both Cl-I R is CH and R is OC H and R is phenyl and R is OOzH and Z is a sulphophenyl or chloro-sulphophenyl.

This invention relates to new compositions for use in dyeing hair and to other keratinic fibers.

It is known in the dyeing of hair to use primary paradiamines in conjunction with couplers whereby various shades of colour can be obtained. However, this procedure is not entirely satisfactory, because the colours obtained are not stable and deteriorate substantially on keeping. Moreover, it is not easy to obtain a predetermined shade by reason of the fact that the final shade results from the superimposition of two dyes, namely a first dye obtained by means of the p-diamine, which in itself has a dyeing eifect, and a second dye obtained by means of the p-diamine and the coupler.

It has also been proposed to use solutions which comprise at least one N-disubstituted p-diamine and a coupler consisting either of a hydroxylated aromatic derivative, a B-diketone or a pyrazolone derivative, the p-diamine and the coupler, taken separately, having only a very low dyeing power, so that the shade obtained results solely from the interaction between the p-diamine and the coupler.

The present invention provides a means of dyeing hair and other keratinic fibres by the conjoint use of p-diamines and certain couplers which produce dyestuffs that have exceptional stability to light for periods of the order of 12 months, which is an ample time with regard to the dyeing of human hair.

On the other hand, although the p-diamines of this invention are capable when used alone, of forming an intense coloration which may range from light brown to black, their association with the couplers of the invention brings about a formation of dyestuffs which are much more rapid than when the p-diamine is used alone. Consequently, the formation of the browns due to the pdiamine is insignificant as compared with the formation of the dye obtained by the p-diamine-coupler association,

and the final shade obtained depends upon this dye and not on the combination of two separate dyes.

The dyeing compositions of the invention comprise a compound of Formula I and at least one coupler of 5 Formulas II, III or IV, the Formula I being:

in which X and Y, which can be the same or different, each represent hydrogen, halogen, alkyl or alkoxy; Y being capable to come at any one of the free positions; Formula II being:

in which:

R represents OCH in the 4-position and R represents H or CH, in the 2-position, or

R represents H or -CH in the 6-position and R in the 3-position is represented by: -CH -OCH NHCOCH NHCH CONH or NHCOCH N(C H or R represents CH in the 6-position and R represents a halogen in the 3- or 5-position; Formula I=II being:

in which R and R are both CH or R represents CH and R represents OC H or R represents phenyl and R represents 00211 and Formula 1V being:

H2O C-OH5 in which: Z represents a phenyl, 3-sulphophenyl, 4-su1- phophenyl or 2-chloro-5-sulphophenyl radical. In Formula I where X or Y is an alkyl or alkoxy radical it is preferably methyl, methoxy, ethyl or ethoxy; and where X or Y is halogen it is preferably chlorine.

An essential feature of the invention resides in the fact that the ratio of the molecular concentration of the pdiamine to the molecular concentration of the coupler or couplers employed should be always less than unity.

The dye compositions of the invention are conveniently used in the form of aqueous solutions having a pH of from 6 to 10. The compositions can contain dyestufis other than those of the invention, for instance ones which may be used under the same conditions as diirect dye- 3 stuffs, for example azo dyestuffs, or dyestuffs produced, in accordance with our French patent application No. 943,485 of Aug. 1, 1963, from the same couplers and an N-disubstituted p-diamine. The compositions can also con tain wetting agents, dispersing agents, penetration agents and other ingredients generally employed for hair dyeing.

The dyeing solutions according to the invention provide a wide range of shades. Thus, use of couplers of Formula II gives blue shades, couplers of the Formula III give yellow shades and couplers of the Formula IV give red shades. Moreover, it is possible by using mixtures of two couplers belonging to the Formulae II, III or IV in various proportions, with the p-diamine, to obtain all shades lying between the colours obtained when each of the couplers is used alone with the p-diamine.

In other words, it will be seen that, by using a limited number of p-diamines and couplers of the invention it is possible by choosing suitable pairs of p-diamines and couplers, and if desired simultaneously using a number of couplers, to obtain a whole range of shades suitable for hair dyes.

Moreover, the dyes formed by the inventive dye solutions have been found to be exceptionally resistant to ageing with no chemical evolution of the dyeing products obtained.

The present invention has also for its object a new process of hair dyeing, said process being essentially characterized by that after having added hydrogen peroxide thereto, one applies on the hair a dyeing solution such as above defined, said hair being afterwards rinsed, shampooed, washed and dried.

The invention is illustrated by the following examples.

EXAMPLE 1 There is prepared a solution containing:

Diamine:

1,2-dimethyl-3,6-diaminobenzene: 1.02 g. Coupler:

2,5-dimethylphenol: 1.22 g. Solvent:

Ethyl alcohol: 5 cc. Sodium hydroxide: 0.02 g. Ammonia solution (22 Be.): 6 cc. Water, q.s. for 50 cc. This solution, which may be kept, is mixed with an equal volume of 6% hydrogen peroxide. The pH is 9.2. The mixture is then applied to white hair for 20 to 30 minutes. After shampooing, the hair is rinsed and dried. There is obtained a greyish purple-blue shade.

EXAMPLE 2 There is prepared a solution containing:

Diamine:

1,2-dimethyl-3,6-diaminobenzene: 1.02 g. Coupler: 4-N-benzoylacetaminobenzoic acid: 9 g. Solvent:

Ammonia solution (22 Be.): 12 cc. Water, q.s. for 50 cc.

This solution is mixed with an equal volume of hydrogen peroxide (6% The pH is 9.0.

The mixture is then applied to white hair for 20 to 30 minutes. After washing, rinsing and drying, a moderate yellow shade is obtained.

EXAMPLE 3 There is prepared a solution containing:

Diamine:

1,2-dimethyl-3,6-diaminobenzene: 1.02 g. Coupler:

l-phenyl-3-methyl-5-pyrazolone: 1.3 g. Solvent:

Ammonia solution (22 Be.): 6 cc.

Water, q.s. for 50 cc.

This solution is mixed with an equal volume of hydrogen peroxide (6%). The pH is 9.5.

The mixture is then applied to white hair for 20 to 30 minutes. After washing, rinsing and drying, there is obtained a light greyish-red shade.

The application of said mixture on yak hair produces the same tint.

EXAMPLE 4 A solution having the composition given in Example 2 and a solution having the composition given in Example 3 are mixed in any proportions. An equal volume of hydrogen peroxide (6%) is then added, and the mixture is applied to white hair for 20 to 30 minutes. When the hair has been washed, rinsed and dried, there is obtained, depending upon the proportions in which the solutions of Examples 2 and 3 are employed, shades ranging from moderate yellow, through shades of orange to faint greyish-red.

EXAMPLE 6 A solution having the composition given in Example 3 and a solution having the composition given in Example 1 are mixed in any proportions. An equal volume of hydrogen peroxide (6%) is added, and the mixture is applied to white hair for 20 to 30 minutes. When the hair has been Washed, rinsed and dried, a dyeing eifect ranging from faint greyish-purple-blue, passing through the purple shades, is obtained.

EXAMPLE 7 There is prepared a solution containing:

Diamine:

2,5-diaminotoluene: 0.61 g. Coupler:

5-chloro-2-methylphenol: 1.95 g. Solvent:

Ethyl alcohol: 5 cc.

Sodium hydroxide: 0.02 g.

Ammonia solution (22 Be.): 6 cc.

Water, q.s. for 50 cc.

This solution is mixed with an equal volume of hydrogen peroxide (6% The pH is 9.2.

The mixture is applied to white hair for 20 to 30 minutes. After washing, rinsing and drying, a dark greenish-blue tint is obtained.

EXAMPLE 8 There is prepared a solution containing:

Diamine:

2,5-diaminotoluene: 0.61 g. Coupler:

Chloro-3-methyl-2-phenol: 1.95 g. Solvent:

Ethyl alcohol: 5 cc.

Sodium hydroxide: 0.02 g.

Ammonia solution (22 Be.): 6 cc.

Water, q.s. for 50 cc.

This solution is mixed with an equal volume of 6% hydrogen peroxide. The pH is 9.2.

The mixture is applied to white hair for 20 to 30 minutes. After washing, rinsing and drying, a blueishgreen shade is obtained.

There is prepared a solution containing:

Diamine:

2,5-diaminoanisol: 0.24 g. Coupler:

3 N (N' diethylcarbamylmethyl)aminophenol:

0.36 g. Solvent:

Ammonia solution (22 Be.): 6 cc. Water, q.s. for 50 cc.

This solution is mixed with an equal volume of 6% hydrogen peroxide. The pH is 9.6.

The mixture is then applied to white hair for 20 to 30 minutes. When the hair has been Washed, rinsed and dried, a dark violet shade is obtained.

EXAMPLE 11 There is prepared a solution containing:

Diamine:

4-chloro-2,S-diaminotoluene: 0.78 g. Coupler:

2-methyl-S-N-carbamylmethylaminophenol: 2.36 g. Solvent:

Ammonia solution (22 Be.): 6 cc. Water, q.s. for 50 cc.

This solution is mixed with an equal volume of 6% hydrogen peroxide. The pH is 9.6.

The mixture is then applied to white hair for 20 to 30 minutes. When the hair has been Washed, rinsed and dried, a greyish purple-red shade is obtained.

EXAMPLE 12 There is prepared a solution containing:

Diamine:

2,S-diamino-4-methoxytoluene: 0.3 g. Coupler:

2-methyl-5-N-(N'-diethylcarbamylmethyl)aminophenol: 0.5 g. Solvent:

Sodium hydroxide: 0.04 g. Ammonia solution (22 Be.): 6 cc. Water, q.s. for 50 cc.

This solution is mixed with an equal volume of 6% hydrogen peroxide. The pH is 9.9.

The mixture is then applied to white hair for 20 to 30 minutes. When the hair has been washed, rinsed and dried, there is obtained a greyish reddish-purple shade.

EXAMPLE 13 There is prepared a solution containing:

Diamine:

2,5-diaminotoluene: 0.61 g.

Coupler:

4-methoxyphenol: 0.45 g.

6 Solvent:

Ethyl alcohol: cc. Sodium hydroxide: 0.02 g. Ammonia solution (22 Be.): 6 cc. Water, q.s. for 50 cc.

This solution is mixed with an equal volume of 6% hydrogen peroxide. The pH is 9.3.

The mixture is then applied to white hair for 20 to 30 minutes. When the hair has been washed, rinsed, and dried, there is obtained a dark blue shade.

EXAMPLE 14 There is prepared a solution containing:

Diamine:

2,5-diamino-4-methoxytoluene: 0.61 g. Coupler:

2-methyl-4-methoxyphenol: 0.50 g. Solvent:

Ethyl alcohol: 5 cc.

Sodium hydroxide: 0.02 g.

Ammonia solution (22 Be.): 6 cc.

Water, q.s. for 50 cc.

This solution is mixed with an equal volume of 6% hydrogen peroxide. The pH is 9.3.

The mixture is then applied to white hair for 20 to 30 minutes. When the hair has been Washed, rinsed, and dried, a dark blue shade is obtained.

EXAMPLE 15 There is prepared a solution containing:

Diamine:

1,4-diaminobenzene hydrochloride: 0.18 g. Coupler:

2acetamino-4methoxyphenol: 0.18 g. Solvent:

Ammonia solution (22 Be.): 6 cc.

Water, q.s. for 50 cc.

This solution is mixed with an equal volume of 6% hydrogen peroxide. The pH is 9.4.

The mixture is then applied to white hair for to minutes. When the hair has been washed, rinsed, and dried, a dark blue shade is obtained.

EXAMPLE 16 There is prepared a solution containing:

Diamine:

1,3-dimethyl-2,S-diaminobenzene: 1.02 g. Coupler:

2-methyl-S-acetaminophenol: 2.0 g. Solvent:

Ammonia solution (22 Be.): 6 cc.

Water, q.s. for cc.

This solution is mixed with an equal volume of hydrogen peroxide (6% The pH is 9.6.

This mixture is applied to white hair for 20 to 30 minutes. When the hair has been Washed, rinsed and dried a greyish purple-blue shade is obtained.

EXAMPLE 17 There is prepared a solution containing:

Diamine:

l,3-dimethyl-2,S-diaminobenzene: 1.02 g. Coupler:

1-pheny1-3-methyl-5-pyrazolone-3'- sulphonic acid: 2 g. Solvent:

Ammonia solution (22 Be.) 8 cc. Water, q.s. for 50 cc. This solution is mixed with an equal volume of hydrogen peroxide (6%). The pH is 9.7.

This mixture is applied to white hair for 20 to 30 minutes. When the hair has been washed, rinsed and dried, a faint reddish-brown shade is obtained.

EXAMPLE 18 There is prepared a solution containing:

Diamine:

2,5-diaminotoluene: 0.61 g. Coupler:

3-acetaminophenol: 2.25 g. Solvent:

(a) Water: 50 cc.

(the pH is 6.4), or (b)NaHCO solution (1.70 g./l.): 50 cc.

(the pH is 6.9), or (c)Na CO solution (2.12 g./l.): 50 cc.

(the pH is 8.4)

Each of these three solutions is mixed with an equal volume of 6% hydrogen peroxide.

Each mixture is applied to white hair for 20 to 30 minutes. When the hair has been washed, rinsed and dried, a bluish-black shade is obtained in each of the three cases.

EXAMPLE 19 There is prepared a solution containing:

Diamine:

2,5-diminotoluene: 0.61 g. Coupler:

3-acetaminophenol: 2.25 g. Solvent:

Aqueous solution of NH (24 g./l.): 50 co.

(the pH is 9.5)

This solution is mixed with an equal volume of 6% hydrogen peroxide.

This mixture is applied to white hair for 20 to 30 minutes. After the hair has been washed, rinsed and dried, a dark greyish-blue shade is obtained.

EXAMPLE 20 There is prepared a solution A containing:

3-;3-(N'-diethylamino) acetaminophenol: 1.11 g. Ammonia solution (220 Be.) 6 cc. Water q.s. for 100 cc.

There is prepared a solution B containing:

2,5-diaminotoluene: 0.25 g. Hydrogen peroxide (20 vol.) 50 cc. Water q.s. for 100 cc.

White hair is treated with a solution A and, after 20 minutes, the hair is rinsed and treated with solution B. After application for 20 minutes, the hair is washed, rinsed and dried. The dyeing effect obtained has a greenish-grey shade.

EXAMPLE 21 There is prepared a solution A containing:

Z-methyI-S-fi-(N-dimethyl)aminoacetaminophenol: 1.18 g.

Ammonia solution (22 Be.): 6 cc.

Water q.s. for 100 cc.

There is prepared a solution B containing:

4-methoxy-2,5-diaminotoluene: 0.3 g. Ammonia solution (22 Be.): 6 cc. Hydrogen peroxide (20 vol.): 50 cc. Water q.s. for 100 cc.

White hair is treated with a solution A and, after 20 minutes, the hair is rinsed and treated with solution B. After application for 20 minutes, the hair is washed, rinsed and dried. The dyeing effect obtained has a pale green shade.

8 EXAMPLE 22 There is prepared a solution containing:

Diamine:

2,5-diaminotoluene: 0.15 g. Coupler:

3-N-benzoylacetaminbenzoic acid: 0.5 g. Solvent:

Ammonia solution (22 Be.) 12 cc.

Water, q.s. for 50 cc.

This solution is mixed with an equal volume of hydrogen peroxide (6%). The pH is 9.

This mixture is applied to white hair for to minutes. When the hair has been washed, rinsed and dried, a moderate yellowish-brown dyeing effect is obtained.

EXAMPLE 23 There is prepared a solution containing:

20 Diamine:

2,5-diaminotoluene: 0.75 g. Coupler:

1-phenyl-3-methyl-5-pyrazolone-4'- sulphonic acid: 1.45 g.

25 Solvent:

Ammonia solution (22 Be.) 8 cc. Water, q.s. for 50 cc.

This solution is mixed with an equal volume of 6% hydrogen peroxide. The pH is 9.5.

The mixture is applied to white hair for 20 to 30 minutes. When the hair has been washed, rinsed and dried, there is obtained a dark reddish-brown dyeing effect.

EXAMPLE 24 There is prepared a solution containing:

EXAMPLE 25 There is prepared a solution containing:

Diamine:

2,5-diamino-4-methoxytoluene: 0.6 g. Coupler:

Ethyl acetylacetate: 5 g. Solvent:

Ammonia solution (22 Be.): 12 cc. Water, q.s. for 50 cc. This solution is mixed with an equal volume of 6% hydrogen peroxide. The pH is 9.5.

This mixture is applied to white hair for 20 to 30 minutes. After washing, rinsing and drying, a moderate yellow dyeing effect is obtained.

EXAMPLE 26 There is prepared a solution containing:

Diamine:

2,5-diaminotoluene: 0.25 g.

Coupler:

Acetylacetone: 2.5

Solvent:

Ammonia solution (22 Be.): 12 cc. Water, q.s. for 50 cc.

This solution is mixed with an equal volume of 6% hydrogen peroxide. The pH is 9.0.

This mixture is applied to white hair for 20 to 30 minutes. The pH is 9.0.

This mixture is applied to white hair for 20 to 30 minutes. After washing, rinsing and drying, there is obtained a moderate olive-brown shade.

If a similar solution containing no coupler is employed, a yellowish-greyish brown shade is obtained.

EXAMPLE 27 There is prepared a solution A containing: Diamine:

1,3dimethyl-2,S-diaminobenzene: 0.68 g. Coupler:

2,5-dimethylphenol: 1.22 g. Solvent:

Ethyl alcohol: cc. Sodium hydroxide: 0.2 g. Ammonia solution (22 Be.): 6 cc. Water, q.s. for 50 cc.

There is thereafter prepared a solution B containing:

Diamine:

[4-amino-B-methyl-N-fi-sulphamidoethylaniline] sulphate: 1.40'g. Coupler:

2,5-dimethylphenol: 1.22 g. Solvent:

Ethyl alcohol: 5 cc. Sodium hydroxide: 0.2 g. Ammonia solution (22 Be.): 6 cc. Water, q.s. for: 50 cc.

Solutions A and B are mixed in any proportions, and there is added to this mixture an equal volume of 6% hydrogen peroxide. The pH is 9.6.

This mixture is then applied to white hair for 20 to 30 minutes. When the hair has been washed, rinsed and dried, there are obtained, depending upon the proportions in which solutions A and B- are employed, dyeing eflects ranging from deep purple-blue to moderate greenish-blue.

EXAMPLE 28 There is prepared a solution A containing:

Diamine:

2,5 -diaminotoluene: 0.61 g. Coupler:

.S-acetaminophenol: 2.2 g. Solvent:

Ammonia solution (22 Be.): 6 cc. Water, q.s. for 50 cc. There is prepared a solution B containing: Diamine:

1,2-dimethyl-3,6-diaminobenzene: 1.02 g. Coupler:

-/3-acetaminophenol: 2.2 g. Solvent:

Ammonia solution (22 Be.) 6 cc. Water, q.s. for 50 cc.

Solutions A and B are mixed in any proportions, and there is added to the mixture obtained an equal volume of 6% hydrogen peroxide. The pH is 9.5.

The mixture is then applied to 'white hair for 20 to 30 minutes. When the hair has been washed, rinsed and dried, there is obtained a dyeing eflect ranging from dark yellowish-blue to dark greenish-blue, depending upon the proportions of A and B.

EXAMPLE 29 There is prepared a solution A containing: Diamine:

1,3-dimethyl-2,S-diaminobenzene: 0.68 g. Coupler:

2,5 -dimethylphenol: 1.22 g.

10 Solvent:

Ethyl alcohol: 5 cc. Sodium hydroxide: 0.2 g. Ammonia solution (22 Be.) 6 cc. Water, q.s. for 50 cc.

There is prepared a solution B containing:

2,4,4-triphydroxyazobenzene: 0.5 g. Sodium hydroxide: 0.08 g. Water, q.s. for 50 cc.

These two solutions A and B are mixed. This mixture is applied to white hair for 20 to 30 minutes. When the hair has been washed, rinsed, and dried, there is obtained,

depending upon the porportions in which the two solutions in which X and Y, which can be the same or different,

each represent hydrogen, halogen, alkyl or alkoxy; Formula II being:

in which:

R represents OCH in the 4-position and R represents H or CH in the 2-position, or

R represents H or CH in the 6-position and R in the 3-position is represented by: CH OCH NHCOCH NHCH CONH NHCH CON (C 5) 2 0r or R represents CH in the 6-position and R represents a halogen in the 3- or 5-position; Formula 111 being:

in which:

R and R are both CH or R represents CH and R represents OC H or R represents phenyl and R represents 1 1 and Formula IV being:

in which:

Z represents phenyl, 3-sulphophenyl, 4-sulphophenyl or 2-chloro-5-sulphophenyl, in aqueous solution having a pH of 6-10.

2. The composition of claim 1, in which the said coupler is selected from the group consisting of 2,5-dimethylphenol, S-chloro 2 methylphenol, chloro-3-methyl-2- phenol, 3 N carbamylmethylaminophenol, 3-N-(N- diethylcarbamylmethyl) aminophenol, 2 methyl-S-N- carbamylmethylaminophenol, 4-methoxyphenol, 2-methyl- 4-methoxyphenol, Z-acetamino 4 methoxyphenol, 2- methyl 5 acetaminophenol, 3-acetaminophenol, 3-6- (N-diethylamino) acetaminophenol, Z-methyI-S-fi-(Ndimethyl)aminoacetaminophenol, 4 N benzoylacetaminobenzoic acid, 3-N-benzoylacetaminobenzoic acid, ethyl acetylacetate, acetyl acetone, 1-pheny1-3-methy1-5-pyrazolone, 1-pheny1-3-methyl-5-pyrazolone 3' sulphonic acid, l-phenyl 3 methyl-S-pyrazolone-4'-sulphonic acid, and 2'-chloro-1-phenyl-3-methyl-5-pyrazolone 5' sulphonic acid.

3. The composition of claim 1, in which said p-diamine is selected from the group consisting of 1,2-dimethyl-3,6- diaminobenzene, 2,5-diaminotoluene, 2,5-diamino-4-methoxytoluene, 2,5-diaminoanisole, 4-chloro-2,5-diaminotoluene, 1,4-diaminobenzene hydrochloride, 1,3-dimethyl- 2,5-diaminobenzene and 4 amino-3-methyl-N- 3-sulphamidoethyl-aniline.

4. The composition of claim 1, which also contains hair treating amounts of hydrogen peroxide.

5. A method of dyeing keratinic fibers, which comprises applying to the fibers coloring amounts of the composition of claim 1.

6. The method of claim 5, wherein said keratinic fibers are human hair.

7. The method of claim 6, in which hydrogen peroxide is applied to the hair along with one of said compounds.

References Cited UNITED STATES PATENTS OTHER REFERENCES Ofiicial Gazette, vol. 652, Nov. 6, 1951, pp. 289-290. Chemical Abstracts, vol. 47: 12065-12066 (1953).

ALBERT T. MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner US. Cl. X.R. 

